Thickened hair dyeing composition com-



United States Patent THICKENED HAIR DYEING COMPOSITION COM- PRISINGPOLYHYDROXYL COMPOUND AND ALKANOLAMINE Wolfgang Max Josef Eckardt andSiegfried Roland Preisinger, Bad Segeberg, Holstein, Germany, assignorsto Lever Brothers Company, New York, N. Y., a corporation of Maine NoDrawing. Original No. 2,769,748, dated November 6, 1956, Serial No.273,352, February 25, 1952. Application for reissue July 1, 1957, SerialNo. 669,915

Claims priority, application Germany February 26, 1951 11 Claims. (Cl.167-88) Matter enclosed in heavy brackets appears in the original patentbut forms no part of this reissue specification; matter printed initalics indicates the additions made by reissue.

. viously used, which hadthe great disadvantage of readily running fromhair during use, redyeing parts of the hair which had already been dyed,and also staining the clothes and face of the user. However, thesethickened compositions, being emulsions or suspensions, have not beentransparent, so that it has been diflicult to observe the progress ofthe dyeing operation. Moreover, due to the use of the oxidation dyesthere is an'increased risk of forming darker patches as a result of lackof uniformity of the hair, whilst originally white patches may not bedyed to a sufficient depth of shade, particularly in the case of coarsehair, which does not absorb dye easily.

In order to overcome the disadvantage of lack of absorption power incoarse hair, a pretreatment with am moniacal hydrogen peroxide has beenrequired. This however due to the high alkalinity of the solution is notbeneficial to the hair keratin. Another expedient has been the provisionof an increased ammonia content in the thickened hair dyeing compositionso as to increase the ability of the coarse hair to absorb the dye. Suchhair dyeing preparations have, however, had a pH of about in order toachieve the desired effect. Here again the alkalinity is high enough tohave a harmful effect on the hair keratin.

By the addition of hair-protecting substances, such as fattyacid-glycerides, higher fatty alcohols, cholesterol or wool wax, tothickened hair dyeing compositions, the harmful effect of excess freeammonia required to increase the absorption of the dye by the hair is toa certain degree overcome. In Swiss Patent No. 197,425, for example, itis proposed to add nonalkaline hair softening carriers, such as higherfatty alcohols and the like, and to abandon the addition of freeammonia. Although the hair is indeed protected from harmful effects, thedyeing is not satisfactory in all instances, and in the use of thiscomposition a pretreatment with alkaline hydrogen peroxide cannot beavoided. When the treatment with alkaline hydrogen peroxide is effected,however, the whole dyeing process becomes troublesome and the. structureof the hair is injured by the alkaline hydrogen peroxide rather than bythe hair dye.

, It has been proposed in German'Patent No. 582,521 that triethanolaminesoaps be included in hair dyeing compositions. These substances,however, only increase the wetting action of the composition and do notenhance the dyeing elfect. The composition is not effective on coarsehair without an alkaline pretreatment.

Attempts have also been made to use triethanolamine in hair dyeingcompbsitions, but satisfactory results have not been obtained, as ispointed out in French Patent No. 900,825, beginning at line 23.

Accordingly, it is an object of the present invention to provide athickened hair dyeing composition'based on oxidation dyes which will dyehair in an unobjectionable manner without a pretreatment with alkalinehydrogen peroxide.

It is also an object of the invention to provide a thickened hair dyeingcomposition which has a relatively low pH, within the range from about 7to about 9, so that the hair keratin is not affected during the dyeingprocess.

In accordance with the instant invention, a hair dyeing composition isprovided containing as essential ingredicuts a polyhydroxyl compoundwhich tends to promote absorption and dyeing and an alkanolamine havinga carbon chain of low molecular weight which tends to equalize thedyeing. This combination of ingredients makes it possible to dispensewith the alkaline peroxide pretreatment heretofore required, even in thecase of coarse hair. Because this combination of components is effectiveat a pH below about 9, to which pH the composition can be adjusted byaddition of an ammonium compound, the harmful effects of a highalkalinity in the hair dyeing composition also are reduced oreliminated. A further advantage of this composition is that hair can bedyed to a uniformly lighter shade than its natural color withoutpretreatment.

In a preferred embodiment, the composition also contains a thickeningagent in an amount to increase its viscosity to a point at which thethickened composition will adhere to the hair for the time required todye it.

The composition is effective with the usual oxidation dyes, i. e.,aromatic diamines or aminophenols, such as p-toluylenediamine,p-aminophenol, and their salts. There is a large group of these usefuldyes known to those skilled in this art and the few mentioned above aremerely illustrative. p-Phenylenediamine is toxic and would notordinarily be used.

Polyhydroxyl compounds which promote absorption and dyeing have from 2to about 12 carbon atoms and from 2 to about 12 hydroxyl groups. Thecompound preferably is an aliphatic polyhydroxyl compound, suchas'sorbitol, ethylene glycol, glycerine, pentaerythritol, xylitol,adonitol, diethylene glycol, mannitol, triethylene glycol, erythritol,dulcitol, propanediol-1,2, butyleneglycol-1,3 and propylene glycol. Theabove examples are all of saturated aliphatic compounds. Unsaturatedaliphatic compounds can also be employed, if desired. Further,polyhydroxyl compounds containing aromatic and cycloaliphatic groups canalso be utilized. The polyhydroxyl compound should be water-soluble or-dis persible.

Alkanolamines having at least one alkylol chain of low molecular weight,up to about 12 carbon atoms, and preferably from 6 to 9 carbon atoms andfrom [6] I to [9] 3 hydroxyl groups are effective dye equalizers.Typical alkylol groups, for example, are methylol, ethylol, andpropylol. The amino nitrogen can be primary, secondary or tertiary, thusbearing at least one alkylol group, up to three alkylol groups, theremaining nitrogen valences being taken with hydrogen or alkyl groups oflow molecular weight such as methyl, ethyl and propyl. These compoundscan be used in the form of their acid salts. Triethanolarnine and itssalts has been found to be very satisfactory and is preferred by reasonof its availablity and cost. However, diethanolamine, tripropa-nolamine,monoethanolamine, monobutylolamine,

dipropanolamine, monopropanolamine, etc., and their salts, also can beused with advantage. Although the literature indicates thatalkanolamines are capable of dyeing hair red, the present research hasnot been able to confirm this.

The pH of the thickened hair dyeing composition according to theinvention should be between about 7 and about 9, which is below that ofthe alkaline thickened hair dyeing compositions used heretofore. Theprotection thus afforded to the hair is particularly noticeable in thegloss and firmness of the hair after treatment. If necessary, the pH canbe adjusted by adding an ammonium compound, i. e., either free ammonia,ammonium hydroxide or an ammonium salt, such as ammonium carbonate,ammonium acetate, ammonium phosphate, ammonium chloride, ammoniumtartrate, ammonium sulfate, ammonium nitrate, ammonium formate, andammonium bromide. If alkanolamine salts are used, am monia or ammoniumhydroxide would be used, but ammonium salts would be added if analkanolamine is employed. The ammonium compound is employed in an amountto provide a pH within the stated range, and preferably approximating8.5 to 9.0.

Taking into account the effect of the polyhydroxl compound to enhancethe absorption and dyeing, and the effect of the alkanolamine toequalize the dyeing, it is usually desirable to employ from about 3 toabout 15% of the alkanolamine, preferably from 4 to 6%, and be tweenabout 2 and about 6% of the polyhydroxyl compound by weight of thecomposition. The amount of ammonium compound required to buffer acomposition containing these proportions of the polyhydroxyl compoundand alkanolamine to a pH of from 7 to 9 usually will lie within therange from about 3 to about In addition to the above ingredients, thehair dye may contain a thickening agent, which may be a watersolublecellulose derivative, such as hydroxyethyl cellulose, methyl celluloseand carboxymethylcellulose (glycolic acid cellulose ethers), usuallyused as the sodium salt, or a water-soluble alginate. These thickeningagents are employed in an amount to transform the composition into asmooth cream or paste which will tend to adhere to the hair for as longa time as desired. The composition desirably flows only slowly, andpreferably flows only under pressure. These thickening agents have theadditional property of producing a. transparent or clear composition,thus facilitating the observation of the progress of the dyeing. Many ofthe compositions thickened with these agents in accordance with theinvention have thixotropic properties. Where transparency is notrequired, however, it is possible to employ other thickening agents,such as starch, wheat flour. Usually from 1 to 10% of a thickening agentwill produce a composition having the desired viscosity.

A small amount of a surface active agent, such as a synthetic detergent,can also be included, usually about 1%, in order to facilitate wettingof the hair by the dye and do away with a subsequent soap shampoo toremove excess dye. As exemplary of such agents, paraflin sulfonates,sulfonated alcohols,'sulfonated fatty acids, fatty alcohol sulfates andfatty acid sulfates can be mentioned. For example, sulfonated coconutoil fatty acids, lauryl sulfate, myristyl sulfate, and sodium palmiticmethyl tauride can be employed.

Small quantities of fatty alcohols or colloidally soluble wool waxderivatives, in particular, condensation products of these substanceswith polyhydroxyalkylene sorbitol, can be added for the care of thehair.

The addition of hydrocarbons, such as paraffin oil, in a small amount,usually less than 1%, will facilitate combing of the dyed hair.

The transparency of the thickened hair dyeing composition of theinvention is not affected by the addition of the above-mentionedsubstances.

The composition is applied to the hair in such a way 4 t as to saturateit thoroughly therewith. This may conveniently be accomplished bycombing or brushing out the hair and by saturating it with a comb wetwith the composition, and by like means known .to those skilled in theart.

The intensity of shade of color obtained primarily depends upon the dyeconcentration and the dyeing temperature. Best results are obtained at atemperature within the range from 20 to 30 C. and when the dyeconcentration does not exceed 5 For most purposes, a dye concentrationwithin the range from 1 to 4% is preferable, but much less than 1% maybe adequate under certain circumstances.

It will be appreciated by those skilled in the art that the intensity ofshade will also be dependent to some extent upon the dyeing temperatureand upon the nature of the dye. For this reason, specific conditionsadapted for every dyeing cannot be given, but those skilled in the artwill know from the above disclosure and the following examples whatconditions to employ in a given case.

The composition and process of the invention is applicable primarily tohuman hair, but may also be employed with animal fibers of all types,including wool.

The following examples of compositions according to the presentinvention are given by way of illustration.

EXAMPLE 1 Parts p-Toluylene diamine sulfate 6.0 p-Aminophenolhydrochloride 0.5 Resorcinol 2.5 Isopropyl alcohol 60.0

The above are mixed together, and to this mixture are added 931 parts of2.4%, sodium carboxymethyl cellulose paste heated to 50 C. andcontaining 4.2% triethanolamine, 2.0% ethylene glycol, 2.4% ammoniumtartrate and 1.0% paraffin sulfonate. A transparent thickened hair dyecomposition is obtained which, developed with oxidizing agents in theusual Way, dyes even hair of low absorptive capacity a uniform darkblonde color without pretreatment. The pH of the hair dyeing compositionmade in this way is 8.7.

EXAMPLE 2 To a hair dye charge according to Example 1 there are added931 parts of 2.4% sodium carboxymethyl cellulose paste heated to 50 C.and containing 5.0% triethanolamine, 3.3% ammonium chloride, 2.2%pentaerythritol and 1.2% paraflin sulfonate. A transparent thickenedhair dye with properties equal to those described in Example 1 isobtained. The pH of this hair dyeing composition is 8.6.

EXAMPLE 3 EXAMPLE 4 To a hair dye charge according to Example 1 thereare added 931 parts of a 2.4% sodium carboxymethyl cellulose pastecontaining 3.8% diethanolamine, 2.4% ammonium tartrate, 2.0% ethyleneglycol, 1.0% of a condensation product of wool wax withpolyhydroxyalkylene sorbitol and 1.0% paraflin sulfonate. A transparentthickened hair dye composition is obtained which absorbs and equalizesWell. The pH of-the hair dyeing composition is 8.9.

The compositions according to the present invention allow hair to bedyed with advantage at a pH substantially below that used at present,thus doing away with the harmful efiects of high alkalinity. Thecompositions are particularly suitable for the dyeing of coarse hair, oflow absorptive power, which hitherto has required either an alkalinepro-treatment or a high alkalinity, in most cases a pH of about 10, inorder to produce satisfactory results. If conventional ingredients areadded, transparent pastes are obtained which can be packed in tubes andapplied with ease.

All parts and percentages are by weight.

The terms alkanolamine and oxidation dye as used in the claims includethe salts thereof.

We claim:

1. A hair dyeing composition comprising an amount up to about 5% of anoxidation hair dye; an alcoholic, non-dyeing absorptionand dye-promotingpolyhydroxyl compound containing from about 2 to about 12 carbon atomsand from about 2 to about 12 hydroxyl groups in an amount within therange from about 2% to about 6%; a dye-equalizing alkanolamine having atleast one alkylol chain of low molecular weight up to about 12 carbonatoms and from [6] 1 to [9] 3 hydroxyl groups in an amount within therange from about 3% to about and a compound capable of supplyingammonium ions in an amount within the range from about 3% to about 5%;the said composition having a pH from 7 to 9.

2. A composition in accordance with claim 1 in which the polyhydroxylcompound is ethylene glycol.

3. A composition in accordance with claim 1 in which the polyhydroxylcompound is pentaerythritol.

4. A composition in accordance with claim 1 in which the polyhydroxylcompound is sorbitol.

5. A composition in accordance with claim 1 in which the alkanolamine istriethanolamine.

6. A composition in accordance with claim 1 in which the alkanolamine isdiethanolamine.

7. A composition in accordance with claim 1 in which the oxidation dyeis an arylene diamine.

8. A composition in accordance with claim 7 in which the oxidation dyeis a p-toluylene diamine.

9. A composition in accordance with claim 1 in which the dye is anaminophenol.

10. A composition in accordance with claim 9 in which the aminophenol isp-aminophenol.

11. A hair dyeing composition which comprises an oxidation hair dye inan amount within the range from about 1% 'to about 4%; an alcoholic,non-dyeing absorptionand dye-promoting polyhydroxyl compound containingfrom about 2 to about 12 carbon atoms and from about 2 to about 12hydroxyl groups in an amount from about 2% to about 6%; a dye-equalizingalkanolamine having at least one alkylol chain of low molecular weightup to about 12 carbon atoms andfrom [6] 1 to [9] 3 hydroxyl groups in anamount within the range from about 4% to about 6%; and a compoundcapable of supplying ammonium ions in an amount within the range fromabout 3% to about 5%; the said composition having a pH from 7 to 9.

References Cited in the file of this patent 1 or the original patentUNITED STATES PATENTS 1,663,202 Kritchevsky Mar. 20, 1928 1,705,818 KernMar. 29, 1929 1,923,178 Ulrich Aug. 22, 19 33 2,042,698 Basch June 2,1936 2,126,964 Kerth Aug. 16, 1938 2,236,970 Goldfarb Apr. 1, 19412,305,356 Luckenbach Dec. 15, 1942 FOREIGN PATENTS 307,948 Great BritainMar. 14, 1929 27,781 Australia Dec. 9, 1930 366,961 Great Britain Feb.9, 1932 466,172 Great Britain May 19, 1937 107,057 Australia Apr. 20,1939 OTHER REFERENCES Cox: Hair Dyes, II," The Analyst, July 1940, pp.393-398, esp. at p. 393.

Evans: Progress in Hair Coloring, Drug and Cosmetic Industry, January1949, pp. 37, 38 and 117-121.

Janistyn: Riechstofie, Seifen, Kosmetika, vol. II, Huthig', Heidelberg,1950, pp. 451-455.

